EP0162385A1 - Procédé pour la préparation de diènes par déshydratation d'aldéhydes - Google Patents

Procédé pour la préparation de diènes par déshydratation d'aldéhydes Download PDF

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Publication number
EP0162385A1
EP0162385A1 EP85105766A EP85105766A EP0162385A1 EP 0162385 A1 EP0162385 A1 EP 0162385A1 EP 85105766 A EP85105766 A EP 85105766A EP 85105766 A EP85105766 A EP 85105766A EP 0162385 A1 EP0162385 A1 EP 0162385A1
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EP
European Patent Office
Prior art keywords
aldehydes
dehydrated
zeolite
zeolites
aldehyde
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EP85105766A
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German (de)
English (en)
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EP0162385B1 (fr
EP0162385B2 (fr
Inventor
Wolfgang Dr. Hoelderich
Franz Dr. Merger
Wolf Dieter Dr. Mross
Gerd Dr. Fouquet
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/86—Borosilicates; Aluminoborosilicates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/88—Ferrosilicates; Ferroaluminosilicates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention relates to a process for the preparation of dienes by dehydrating aldehydes using zeolites as catalysts.
  • Dienes are sought after chemical compounds because of their versatile uses. You need them e.g. in the rubber and plastics industry as well as starting and intermediate compounds in diverse organic reactions.
  • the preparation of dienes from aldehydes by simple dehydration is desirable since the aldehydes e.g. are easily accessible via oxo synthesis.
  • the catalysts used are e.g. Acids such as phosphoric acid (DE-OS 21 63 396), boron phosphates (EP 80 449) and ammonium aluminum sulfates (GB 2 063 297) are used. With these processes, water vapor dilution is disadvantageous. In addition, regeneration of the catalysts deactivated by coke deposition is difficult or impossible to carry out.
  • the new process achieves high selectivities, sales and downtimes. Another advantage is that high selectivities are obtained with a long running time of the catalyst even in the absence of water vapor. It is also advantageous that the catalysts to be used according to the invention can be easily regenerated with air after they have been deactivated by coke formation.
  • Aldehydes which can be dehydrated to dienes by the process of the invention are, for example, aldehydes of the formula in which the radicals R 1 , R2 and R 3 are the same or different and each represent an aliphatic, cycloaliphatic, aromatic or heterocyclic radical having 1 to 10 carbon atoms and R 1 and R 2 can also represent hydrogen atoms. Hee / P
  • Aliphatic residues are e.g. straight-chain or branched alkyl radicals with 1 to 8 carbon atoms, cycloaliphatic radicals are e.g. Cyclohexyl residues and aromatic residues are e.g. Phenyl residues.
  • R 4 and R 5 are the same or different.
  • R 4 denotes an alkyl radical with 1 to 3 C atoms or a hydrogen atom and
  • R 5 denotes an alkyl radical with 1 to 8 C atoms or a hydrocarbon radical which together with R 4 forms a cyclohexyl radical.
  • Suitable aldehydes of the type mentioned are particularly those which carry a hydrogen atom on an alpha-carbon atom. Examples include the following aldehydes: butanal, 2-methylbutanal, 2-methylpentanal, 2-ethylhexanal, pivalinaldehyde, 2-benzylpropanal, 2-ethylbutanal, cyclohexylaldehyde and isovaleraldehyde.
  • the starting compounds can be prepared, for example, from olefins by Qxosynthesis. For example, 2-Methylbutanal obtained by hydroformylation of butene-2.
  • the catalysts used for the dehydration of the aldehydes to the dienes zeolites according to the invention.
  • Zeolites are crystalline aluminosilicates, which have a highly ordered structure with a rigid three-dimensional network of SiO 4 and Al0 4 tetrahedra, which are connected by common oxygen atoms. The ratio of Si and Al atoms to oxygen is 1: 2.
  • the electrovalence of the tetrahedra containing aluminum is compensated for by the inclusion of cations in the crystal, for example an alkali metal or hydrogen ion. A cation exchange is possible.
  • the spaces between the tetrahedra are occupied by drying or calcining water molecules before dehydration.
  • the zeolites can also contain trivalent elements such as B, Ga, Fe or Cr instead of aluminum and tetravalent elements such as Ge instead of silicon.
  • Zeolites of the pentasil type are preferably used as catalysts. These zeolites can have different chemical compositions. These are alumino, boro, iron, gallium, chromium, arsenic and bismuth silicate zeolites or their mixtures as well as alumino, boro, gallium and iron germanate zeolites or their mixtures. Alumino, borosilicate and iron silicate zeolites of the pentasil type are particularly preferred.
  • the aluminosilicate zeolite is made, for example, from an aluminum compound, preferably Al (OH) 3 or Al 2 (SO 4 ) 3 , and a silicon component, preferably highly disperse silicon dioxide in aqueous amine solution, in particular 1,6-hexanediamine or 1,3-propanediamine or triethylenetetramine - Solution with and without addition of alkali or alkaline earth at 100 to 220 ° C under autogenous pressure.
  • the aluminosilicate zeolites obtained contain an SiO 2 / Al 2 O 3 ratio of 10 to 40,000, depending on the amount of feedstock selected.
  • the aluminosilicate zeolites can also be prepared in an ethereal medium, such as diethylene glycol dimethyl ether, in an alcoholic medium, such as methanol or 1,4-butanediol, or in water.
  • the borosilicate zeolite is e.g. synthesized at 90 to 200 ° C under autogenous pressure by using a boron compound e.g. H3B03, with a silicon compound, preferably with highly disperse silicon dioxide in aqueous amine solution, in particular in 1,6-hexanediamine or 1,3-propanediamine or triethylenetetramine solution with and without addition of alkali metal or alkaline earth metal.
  • aqueous amine solution an ethereal amine solution, e.g. with diethylene glycol dimethyl ether, or an alcoholic solution, e.g. use with 1,6-hexanediol as solvent.
  • the iron silicate zeolite is obtained, for example, from an iron compound, preferably Fe 2 (S0 4 ) 3 and a silicon compound, preferably from highly disperse silicon dioxide in aqueous amine solution, in particular 1,6-hexanediamine, with and without addition of alkali metal or alkaline earth metal at 100 to 200 ° C. under autogenous pressure.
  • an iron compound preferably Fe 2 (S0 4 ) 3 and a silicon compound, preferably from highly disperse silicon dioxide in aqueous amine solution, in particular 1,6-hexanediamine, with and without addition of alkali metal or alkaline earth metal at 100 to 200 ° C. under autogenous pressure.
  • the alumino, borosilicate and iron silicate zeolites thus produced can, after their isolation, drying at 100 to 160 ° C., preferably 110 ° C., and calcination at 450 to 550 ° C., preferably 500 ° C., with a binder in a ratio of 90:10 up to 40:60% by weight into strands or tablets.
  • Various aluminum oxides preferably boehmite, amorphous aluminosilicates with an SiO 2 / Al 2 O 3 ratio of 25:75 to 95: 5, preferably 75:25, silicon dioxide, preferably highly disperse Si0 2 , 3 mixtures of highly disperse Si0 2 and, are suitable as binders highly disperse A1 2 0 3 , highly disperse Ti0 2 and clay.
  • the extrudates or pellets at 110 ° C / 16 h and dried at 500 C are c / 16 calcined.
  • Such catalysts can be produced particularly advantageously by deforming the isolated aluminosilicate or borosilicate or iron silicate zeolite directly after drying and subjecting it to calcination for the first time after shaping. From the catalysts deformed into strands, eddy material in the size of 0.1 to 0.5 mm can be obtained by grinding and sieving.
  • the alumino, borosilicate and iron silicate zeolites can also be used in pure form, without binders, as strands or tablets.
  • Y-type aluminosilicate zeolites which are prepared from silica sol (29% SiO 2 ) and sodium aluminate in an aqueous medium can also be used as catalysts. These aluminosilicate zeolites can also be deformed with binders before they are used. The zeolites can also be of the mordenite type.
  • the zeolite is not in the catalytically preferred acidic H form, but is e.g. in the Na form, then this can be converted completely or partially into the desired H form by ion exchange with ammonium ions and subsequent calcination or by treatment with acids.
  • Different modifications can also be carried out on the zeolites to increase the selectivity, the service life and the number of regenerations.
  • a suitable modification is e.g.
  • the undeformed or deformed zeolite can be ion-exchanged or impregnated with alkali metals such as Na — provided the alkali form of the zeolite is not already synthesized — with alkaline earths such as Ca, Mg and earth metals such as B, Tl.
  • alkali metals such as Na
  • alkaline earths such as Ca, Mg and earth metals such as B, Tl.
  • doping of the zeolites with transition metals such as Mo, W, Fe, Zn, Cu, with noble metals such as Pd and with rare earth metals such as Ce, La is particularly advantageous.
  • such modified contacts are e.g. so that the deformed pentasil zeolite is placed in a riser and at 20 to 100 ° C e.g. an aqueous solution of a halide or a nitrate of the above-described metals is passed over it.
  • ion exchange can e.g. on the hydrogen, ammonium and alkali form of the zeolite.
  • the metal deposition on the zeolites can e.g. also so that the zeolitic material e.g. impregnated with a halide, a nitrate or an oxide of the above-described metals in aqueous or alcoholic solution. Both ion exchange and impregnation are followed at least by drying and optionally by repeated calcination.
  • one proceeds, for example, by dissolving molybdenum oxide (Mo03) or tungstic acid (H 2 W0 4 ) or Ce (N0 3 ) 3 x6H 2 0 in water - at least for the most part.
  • Mo03 molybdenum oxide
  • tungstic acid H 2 W0 4
  • Ce N0 3
  • 3 x6H 2 0 water - at least for the most part.
  • the extruded or non-extruded zeolite is then soaked with this solution for a certain time, about 30 minutes.
  • the supernatant solution is freed of water on a rotary evaporator.
  • the soaked zeolite is then dried at approximately 150 ° C. and calcined at approximately 550 ° C. This impregnation process can be carried out several times in succession in order to set the desired metal content.
  • An ion exchange of the zeolite present in the H form can be carried out by placing the zeolite in strands or pellets in a column and, for example, an ammoniacal Pd (N0 3 ) 2 solution at a slightly elevated temperature between 30 and 80 ° C conducts in the circuit for 15 to 20 h. Then it is washed out with water, dried at approx. 150 ° C and calcined at approx. 550 ° C.
  • Another possibility for modification consists in subjecting the zeolitic material - deformed or undeformed - to treatment with acids such as hydrochloric acid, hydrofluoric acid and phosphoric acid and / or with steam. It is advantageous to go e.g. so that the zeolite powder is treated with hydrofluoric acid (0.001 n to 2 n, preferably 0.05 n to 0.5 n) for 1 to 3 hours under reflux before it is deformed. After filtering off and washing out, it is dried at 100 to 160 ° C. and calcined at 400 to 550 ° C. Treatment of the zeolites with hydrochloric acid after they have been deformed with a binder may also be expedient.
  • the zeolite is e.g.
  • the zeolite can also be modified by applying phosphorus compounds such as trimethoxyphosphate.
  • the zeolitic catalysts After the zeolitic catalysts have been deactivated, which can occur in the process of the invention by coke separation, these can be easily removed by burning off the coke deposit with air or with an air / N 2 mixture at 400 to 550 ° C., preferably 500 ° C. regenerate, giving them back their initial activity.
  • the activity of the catalyst for optimum selectivity of the desired reaction product can also be adjusted by partial coking (pre-coke). If the dehydration is carried out in the presence of gases such as hydrogen, nitrogen and steam, the product composition and service life of the catalyst can be influenced.
  • the catalysts are optionally available as 2 to 4 mm strands, as tablets 3 to 5 mm in diameter, as a powder with particle sizes from 0.3 to n ; 5 mm or (as swirl contact) from 0.1 to 0.5 mm.
  • the dehydration of the aldehydes to the dienes is preferably carried out on the zeolites at temperatures of 150 to 600 ° C., in particular at 300 to 500 ° C.
  • the load (WHSV) is 0.1 to 20, preferably 0.5 to 5 g of aldehyde per gram of catalyst per hour.
  • the process can be batch or continuous, depressurized or under pressure, e.g. in a flow reactor, stirred tank or vortex reactor. Unreacted aldehydes can optionally be separated by distillation from the dienes formed and used again for the reaction according to the invention.
  • the respective aldehyde was introduced for the purpose of dehydration to diene under isothermal conditions in a tubular reactor (spiral shape, inside diameter 0.6 cm and length of 90 cm) and passed in the gas phase at temperatures of 350 to 450 ° C over a zeolite catalyst.
  • the reaction products obtained were worked up by distillation and characterized by boiling point, refractive index and NMR spectra.
  • the quantitative determination of the reaction products and the starting products was carried out by gas chromatography.
  • the type of catalyst, the temperature, the load (WHSV), the conversion and the selectivity can be found in the following table.
  • Example 5 shows the influence of temperature on conversion and selectivity.
  • the catalysts used were produced as follows:
  • the catalyst was in a hydrothermal synthesis from 64 g Si0 2 (highly disperse silica), 12.2 g H 3 BO 3 , 800 g of an aqueous hexanediamine solution (mixture 50:50 wt.%) At 170 ° C under autogenous pressure in a stirred autoclave. After filtering off and washing out, the crystalline reaction product was dried at 100 ° C./24 h and calcined at 500 ° C./24 h. A pentasil-type borosilicate zeolite was obtained which contained 94.2% by weight of SiO 2 and 2.32% by weight of B 2 0 3 . 2 mm strands were produced from this zeolite, which were dried at 100 ° C. and calcined at 500 ° C. for 24 hours.
  • An aluminosilicate zeolite of the pentasil type was prepared under hydrothermal conditions at autogenous pressure and 150 ° C. from 65 g highly disperse SiO 2 , 20.3 g Al 2 (SO 4 ) 3 x 18H 2 0 in 1 kg of an aqueous 1,6-hexanediamine Solution (mixture 50:50 wt.%) Prepared in a stirred autoclave. After filtering off and washing out, the crystalline reaction product was dried at 110 ° C./24 h and calcined at 500 ° C./24 h. This aluminosilicate zeolite contained 91.6% by weight Si0 2 and 4.6% by weight Al 2 O 3 .
  • this aluminosilicate zeolite were refluxed with 140 ml 0.1N HF for 1 h. After filtering off, the mixture was washed with water until neutral, dried at 110 ° C./16 h and calcined at 500 ° C./5 h.
  • This zeolite was shaped with amorphous aluminosilicate (75% by weight SiO 2 and 25% by weight A1 2 0 3 ) in a weight ratio of 60:40 to 2 mm strands, dried at 110 ° C./16 h and at 500 ° C./24 h calcined.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP85105766A 1984-05-24 1985-05-10 Procédé pour la préparation de diènes par déshydratation d'aldéhydes Expired - Lifetime EP0162385B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843419379 DE3419379A1 (de) 1984-05-24 1984-05-24 Verfahren zur herstellung von dienen durch dehydratisierung von aldehyden
DE3419379 1984-05-24

Publications (3)

Publication Number Publication Date
EP0162385A1 true EP0162385A1 (fr) 1985-11-27
EP0162385B1 EP0162385B1 (fr) 1987-09-23
EP0162385B2 EP0162385B2 (fr) 1991-08-14

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EP85105766A Expired - Lifetime EP0162385B2 (fr) 1984-05-24 1985-05-10 Procédé pour la préparation de diènes par déshydratation d'aldéhydes

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US (1) US4560822A (fr)
EP (1) EP0162385B2 (fr)
JP (1) JPS6125A (fr)
CA (1) CA1230618A (fr)
DE (2) DE3419379A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0209785A2 (fr) * 1985-07-23 1987-01-28 BASF Aktiengesellschaft Procédé pour la préparation de la méthylisopropylcétone et de l'isoprène
EP0219042A2 (fr) * 1985-10-15 1987-04-22 BASF Aktiengesellschaft Procédé pour la fabrication de diènes par la déshydratation d'aldéhydes
EP0463748A1 (fr) * 1990-06-04 1992-01-02 Enichem Elastomers Limited Procédé pour la préparation de diènes conjugués
CN1076218C (zh) * 1996-07-25 2001-12-19 中国科学院大连化学物理研究所 一步法合成2,5－二甲基－2,4－己二烯反应用催化剂及应用

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4628140A (en) * 1986-03-03 1986-12-09 The Goodyear Tire & Rubber Company Process for the production of dienes from aldehydes
US4734538A (en) * 1986-12-24 1988-03-29 Union Carbide Corporation Process for the production of dienes
DE102006037314A1 (de) * 2006-08-08 2008-02-14 Süd-Chemie AG Verwendung eines Katalysators auf Basis von Zeolithen bei der Umsetzung von Oxygenaten zu niederen Olefinen sowie Verfahren hierzu
WO2019131890A1 (fr) * 2017-12-27 2019-07-04 積水化学工業株式会社 Catalyseur ainsi que procédé de fabrication de celui-ci, et procédé de fabrication de composé diène mettant en oeuvre ledit catalyseur
EP3735401B1 (fr) 2018-01-04 2023-04-26 GEVO, Inc. Valorisation de mélanges d'huile de fusel sur des catalyseurs hétérogènes en produits chimiques renouvelables de plus grande valeur
US11976017B2 (en) 2019-12-19 2024-05-07 Dow Technology Investments Llc Processes for preparing isoprene and mono-olefins comprising at least six carbon atoms
KR20220097223A (ko) 2020-12-31 2022-07-07 주식회사 피플카 커뮤니티 기반 모빌리티 서비스를 위한 전자 장치, 이를 포함하는 시스템 및 차량 공유 방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2163396A1 (de) * 1971-12-21 1973-06-28 Erdoelchemie Gmbh Verfahren zur katalytischen gewinnung von dienen aus aldehyden
JPS5726A (en) * 1980-05-29 1982-01-05 Mitsubishi Electric Corp Line filter
GB2093060A (en) * 1981-01-05 1982-08-25 Int Synthetic Rubber The Co Lt Preparation of Substituted Dienes

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2421361A (en) * 1942-09-29 1947-05-27 Carbide & Carbon Chem Corp Process for making diolefins
US2421762A (en) * 1944-08-24 1947-06-10 Short Frank Hand grenade
GB2063297B (en) * 1979-11-16 1983-07-20 Int Synthetic Rubber Preparation of conjugated dienes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2163396A1 (de) * 1971-12-21 1973-06-28 Erdoelchemie Gmbh Verfahren zur katalytischen gewinnung von dienen aus aldehyden
JPS5726A (en) * 1980-05-29 1982-01-05 Mitsubishi Electric Corp Line filter
GB2093060A (en) * 1981-01-05 1982-08-25 Int Synthetic Rubber The Co Lt Preparation of Substituted Dienes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 006, no. 094 (C - ) 2 June 1982 (1982-06-02) *
SOVIET INVENTIONS ILLUSTRATED, Sektion Ch, Woche D 23, 15. Juli 1981 DERWENT PUBLICATIONS LTD., London, A 41 E 17; & SU-A-1765251 (AZERB AZIZBEKOV PETROCHE) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0209785A2 (fr) * 1985-07-23 1987-01-28 BASF Aktiengesellschaft Procédé pour la préparation de la méthylisopropylcétone et de l'isoprène
EP0209785A3 (en) * 1985-07-23 1987-06-10 Basf Aktiengesellschaft Process for the preparation of methylisobutylketone and isoprene
EP0219042A2 (fr) * 1985-10-15 1987-04-22 BASF Aktiengesellschaft Procédé pour la fabrication de diènes par la déshydratation d'aldéhydes
EP0219042A3 (en) * 1985-10-15 1987-10-21 Basf Aktiengesellschaft Process for the production of dienes by the dehydration of aldehydes
EP0463748A1 (fr) * 1990-06-04 1992-01-02 Enichem Elastomers Limited Procédé pour la préparation de diènes conjugués
CN1076218C (zh) * 1996-07-25 2001-12-19 中国科学院大连化学物理研究所 一步法合成2,5－二甲基－2,4－己二烯反应用催化剂及应用

Also Published As

Publication number Publication date
DE3419379A1 (de) 1985-11-28
EP0162385B1 (fr) 1987-09-23
US4560822A (en) 1985-12-24
DE3560673D1 (en) 1987-10-29
EP0162385B2 (fr) 1991-08-14
JPS6125A (ja) 1986-01-06
CA1230618A (fr) 1987-12-22

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